Synthesis, purification, and complexation of polyamine ligand mixtures.
| dc.contributor.author | Lilley, Sarah Ellen | |
| dc.date.accessioned | 2020-08-24T03:06:07Z | |
| dc.date.available | 2020-08-24T03:06:07Z | |
| dc.date.issued | 2020 | en |
| dc.description.abstract | This work focussed on synthesis of polyamine ligands by functionalisation of a linear hexamine starting material with 1,8-naphthalic anhydride to create two naphthalimide groups. This ligand was designed to be incorporated into a heterodinuclear redox-activated prodrug complex of cisplatin and cobalt. The naphthalimide groups were intended to block associative ligand exchange on the platinum centre that would otherwise result in premature release or inactivation of the prodrug. Reaction of the impure 3,6,9,12-tetraazatetradecane-1,14-diamine starting material with 1,8- naphthalic anhydride gave a complex mixture of products, including branched and piperazine compounds and trinaphthalimides. Efforts were made to separate the desired linear dinaphthalimide product from the side products using a process of purification by complexation. This purification strategy relied on the desired compound and its complex having different properties to any side products that might lead to their separation. The copper can then be removed from the separated complex using EDTA to recover the desired dinaphthalimide ligand. Throughout this process, the copper complex of the dinaphthalimide ligand was successfully synthesised and followed by copper removal. This process led to enrichment of the desired ligand material in the reaction fractions following removal of copper with EDTA. Attempts were made to synthesise cobalt complexes from the dinaphthalimide ligand containing mixtures. ESI-MS evidence was obtained for both the [Co(C₃₄H₃₆N₆O₄)CO₃]+ and [Co(C₃₄H₃₆N₆O₄)(NO₂)₂]+ complexes. Additionally, a deprotonated ligand cobalt complex was observed by ESI-MS. Structural elucidation of a copper complex of a trinaphthalimide ligand was also performed based on crystallographic data. The trinaphthalimide ligand was synthesised from a branched isomeric impurity in a new hexamine starting material, 3,7,10,14-tetraazahexadecane-1,16- diamine. The crystal structure showed the copper centre was also coordinated to a sulfate anion in a bidentate fashion forming a five-coordinate square planar centre. | en |
| dc.identifier.uri | https://hdl.handle.net/10092/100933 | |
| dc.identifier.uri | http://dx.doi.org/10.26021/1139 | |
| dc.language | English | |
| dc.language.iso | en | |
| dc.publisher | University of Canterbury | en |
| dc.rights | All Rights Reserved | en |
| dc.rights.uri | https://canterbury.libguides.com/rights/theses | en |
| dc.title | Synthesis, purification, and complexation of polyamine ligand mixtures. | en |
| dc.type | Theses / Dissertations | en |
| thesis.degree.discipline | Chemistry | en |
| thesis.degree.grantor | University of Canterbury | en |
| thesis.degree.level | Masters | en |
| thesis.degree.name | Master of Science | en |
| uc.bibnumber | 2941686 | |
| uc.college | Faculty of Science | en |